Application of ring-polymer molecular dynamics to electronically nonadiabatic excess electron dynamics in water clusters: Importance of nuclear quantum effects

The ring-polymer molecular dynamics (RPMD) method was applied to the real-time excess electron dynamics in water clusters within a one-electron pseudo-potential model, where the excess electron motion is described with the grid-based wave function while nuclear motions of water are described with RPMD. We have simulated electronically non-adiabatic relaxation dynamics associated with s → p excitation of an excess electron in the (H2O)50− water anion cluster. We compared the RPMD results to the corresponding results obtained from classical MD simulations. It was found that nuclear quantum effects are playing a very important role in determining nonadiabatic relaxation time.